Local structural investigation of non-crystalline materials at high pressure: the case of GeO₂glass

Local structures play a crucial role in the structural polyamorphism and novel electronic properties of amorphous materials, but their accurate measurement at high pressure remains a formidable challenge. In this article, we use the local structure of network-forming GeO₂glass as an example, to present our recent approaches and advances in high-energy x-ray diffraction, high-pressure x-ray absorption fine structure, andab initiofirst-principles density functional theory calculations and simulations. Although GeO₂glass is one of the best studied materials in the field of high pressure research due to its importance in glass theory and geophysical significance, there are still some long-standing puzzles, such as the existence of appreciable distinct fivefold^[5]Ge coordination at low pressure and the sixfold-plus^[6+]Ge coordination at ultrahigh pressure. Our work sheds light on the origin of pressure-induced polyamorphism of GeO₂glass, and the^[5]Ge polyhedral units may be the dominant species in the densification mechanism of network-forming glasses from tetrahedral to octahedral amorphous structures.